Dental Glass-Reinforced Composite for Caries Inhibition: Calcium

Phosphate Ion Release and Mechanical Properties

Hockin H. K. Xu, Jennifer L. Moreau
Department of Endodontics, Prosthodontics and Operative Dentistry, University of Maryland
Dental School, Baltimore, Maryland 21201

Received 1 May 2009; revised 20 July 2009; accepted 27 July 2009

Published online 6 October 2009 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/jbm.b.31519

Abstract: The two main challenges facing dental composite restorations are secondary caries
and bulk fracture. Previous studies developed whisker-reinforced Ca-PO4 composites that
were relatively opaque. The objective of this study was to develop an esthetic glass particle-
reinforced, photo-cured calcium phosphate composite. Tetracalcium phosphate (TTCP)
particles were incorporated into a resin for Ca and PO4 release, while glass particles provided
reinforcement. Ion release and mechanical properties were measured after immersion in
solutions with pH of 7, 5.5, and 4. For the composite containing 40% mass fraction of TTCP,
incorporating glass fillers increased the strength (p < 0.05). Flexural strength (Mean 6 SD;
n 5 6) at 30% glass was 99 6 18 MPa, higher than 54 6 20 MPa at 0% glass (p < 0.05). Elastic
modulus was 11 GPa at 30% glass, compared to 2 GPa without glass. At 28 days, the released
Ca ion concentration was 4.61 6 0.18 mmol/L at pH of 4, much higher than 1.14 6 0.07 at pH
of 5.5, and 0.27 6 0.01 at pH of 7 (p < 0.05). PO4 release was also dramatically increased at
cariogenic, acidic pH. The TTCP-glass composite had strength 2–3 fold that of a resin-
modified glass ionomer control. In conclusion, the photo-cured TTCP-glass composite was
‘‘smart’’ and substantially increased the Ca and PO4 release when the pH was reduced from
neutral to a cariogenic pH of 4, when these ions are most needed to inhibit tooth caries. Its
mechanical properties were significantly higher than previous Ca, PO4, and fluoride releasing
restoratives. Hence, the photo-cured TTCP-glass composite may have potential to provide the
necessary combination of load-bearing and caries-inhibiting capabilities. ' 2009 Wiley
Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 92B: 332–340, 2010

Keywords: dental composite; tetracalcium phosphate; smart material; tooth caries inhibition;
Ca and PO4 ion release

INTRODUCTION reason for the replacement of existing restorations.21

Approximately 200 million dental restorations are placed
annually in the U S.1 Resin composites are widely used for
tooth cavity restorations due to their esthetics, direct-filling
capability, and improved longevity. Composites are com-
posed of fillers in an acrylic matrix that is polymerized to
form a solid restoration.2–7 Previous studies have improved
the resin compositions and cure conditions, and reduced the
polymerization shrinkage.8–13 In addition, extensive efforts
have been undertaken to enhance the fracture and wear re-
sistance of the composites.14–18 Despite these meritorious
improvements, recent reports still show that ‘‘The two main
challenges are secondary caries and bulk fracture.’’19,20
Secondary caries at the tooth-restoration margins is a major
Correspondence to: H.H.K. Xu (e-mail: hxu@umaryland.edu)
Contract grant sponsor: NIH R01; Contract grant numbers: DE14190, DE17974;
Contract grant sponsors: Maryland Nano-Biotechnology Initiative Award, University
of Maryland Dental School.
' 2009 Wiley Periodicals, Inc.
332
Replacement of restorations accounts for 50–70% of all
restorations.22,23 Replacement dentistry costs about $5 bil-
lion annually in the United States alone.24
An effective approach to addressing the caries problem
was to develop calcium and phosphate (CaP) ion-releasing
materials. CaP particles were filled into the resin, and
the resulting composite released supersaturating levels
of Ca and PO4 ions, which formed hydroxyapatite
[Ca10(PO4)6(OH)2], the putative mineral in enamel and
dentin.25–29 Indeed, several CaP materials were shown to
effectively remineralize enamel and dentin lesions in
vitro.25,28 However, while they addressed the caries prob-
lem, they did not address the restoration fracture problem.
This was because these CaP materials had flexural strengths
of only half that of unfilled resin.26 It was recognized that
such low strengths were ‘‘inadequate to make these compo-
sites acceptable as bulk restoratives.’’27
To address both the tooth caries and the restoration frac-
ture problems, both CaP fillers and reinforcing fillers were
incorporated into the resin to develop load-bearing, Ca and
 DENTAL CALCIUM PHOSPHATE COMPOSITE
PO4 releasing composites.30–32 Besides the load-bearing
issue, another important factor that needs to be considered
is that the oral plaque pH after a sucrose rinse can decrease
to 4.5 or even 4.33,34 A plaque pH of higher than 6 is con-
sidered to be the safe area, a plaque pH of 6.0 to 5.5 is the
potentially cariogenic area, and pH of 5.5 to 4 is the cario-
genic or danger area for cavity formation. Therefore, it is
desirable for the CaP composite to be ‘‘smart,’’ to increase
the release of caries-inhibiting ions at lower pH, when the
Ca and PO4 ions are most needed. Such ion release trig-
gered by a local pH drop may help prevent demineraliza-
tion in tooth structures contiguous to the smart composite
restoration. Therefore, in a recent study, tetracalcium phos-
phate [TTCP: Ca4(PO4)2O] composite was developed and
shown to be smart to substantially increase the ion release
at cariogenic pH.35 TTCP is a compound used in bone
cements,36 tissue engineering scaffolds,37 and dental mate-
rials.28 TTCP is the most alkaline among all CaP com-
pounds,36 and is promising in buffering harmful acids and
inhibiting tooth caries. However, that recent study used
whiskers as the reinforcing filler, resulting in an opaque
paste that was not sufficiently esthetic.35 Further study is
needed to develop a TTCP composite reinforced with den-
tal glass particles that is esthetic and translucent, and the
paste can be photo-cured.
Accordingly, the objectives of this study were to de-
velop a ‘‘smart’’ TTCP composite reinforced with esthetic
dental glass particles, and to investigate the effects of solu-
tion pH on composite ion release and mechanical proper-
ties. It was hypothesized that: (1) The photo-cured TTCP-
glass composite would be smart and able to increase its ion
release when the pH is decreased; (2) Glass particle rein-
forcement would significantly increase the mechanical
properties of the TTCP composite, which would be signifi-
cantly stronger than previously-reported ion-releasing
restoratives.
MATERIALS AND METHODS
TTCP and Glass Fillers
TTCP was synthesized from a solid-state reaction between
CaHPO4 and CaCO3 (Baker Chemical, Phillipsburg, NJ),
which were mixed and heated at 15008C for 6 h in a fur-
nace (Thermolyne, Dubuque, IA).36,37 The mixture was
quenched to room temperature and ground in a blender
(Dynamics, New Hartford, CT). The powder was then
sieved to obtain TTCP particles with sizes of 1.5–60 lm,
with a median of 16 lm. This TTCP powder was then
ground in 95% ethanol with a ball-mill (Retsch, Newtown,
PA) for 24 h. The particle size distribution was measured
via a sedimentation method with the use of a centrifugal
particle analyzer (SA-CP3, Shimazu, Kyoto, Japan). This
yielded a particle size range of 0.2–3.0 lm, with a median
of 0.8 lm. This TTCP powder was moderately finer than
the TTCP used in a previous study.35
Journal of Biomedical Materials Research Part B: Applied Biomaterials
333
The glass particles were a barium boroaluminosilicate
glass (median diameter 5 1.4 lm, Caulk/Dentsply, Milford,
DE), selected because it is a typical dental glass filler simi-
lar to those in a hybrid composite (TPH, Cault/Dentsply).
The purpose was to develop a model composite; the proc-
essing parameters can then be applied to the use of other
glass fillers. The glass particles were silanized with 4% 3-
methacryloxypropyltrimethoxysilane and 2% n-propylamine
(mass %).38,39
Resin Composite Fabrication
A resin of Bis-GMA (bisphenol glycidyl dimethacrylate)
and TEGDMA (triethylene glycol dimethacrylate) at 1:1
mass ratio was rendered light-curable with 0.2% camphor-
quinone and 0.8% ethyl 4-N,N-dimethylaminobenzoate.
Four groups of specimens were fabricated. The purpose
of Group 1 was to examine the effect of TTCP filler level
on the mechanical properties of the photo-cured composite.
Only TTCP was used as fillers in the resin, without glass
fillers. The TTCP filler levels (mass fraction) in the resin
were: 0%, 20%, 40%, 60%, and 70%.
The fillers were mixed with the resin and the paste was
placed into a stainless steel mold of 2 mm 3 2 mm 3 25
mm. No de-gas procedure was performed for the experi-
mental composite pastes and the control pastes. All the ex-
perimental composite pastes and the control pastes were
photo-cured (Triad 2000, Dentsply, York, PA) for 1 min on
each side. The cured specimens were incubated at 378C for
24 h prior to testing.
The purpose of Group 2 was to investigate the effects of
glass reinforcement on composite mechanical properties.
The total fillers in the resin 5 TTCP 1 glass. An interme-
diate TTCP filler mass fraction of 40% was selected to
leave room in the resin for glass reinforcement.
The glass filler mass fractions were: 0%, 10%, 20%,
30%, and 35%. Hence the TTCP 1 glass filler level 5
40%, 50%, 60%, 70%, and 75%, respectively. Glass filler
levels higher than 35% were not used because the compos-
ite paste became relatively dry. The specimens were photo-
cured in the same manner as described for Group 1.
The purpose of Group 3 was to investigate the effect of
solution pH on mechanical properties of the composite
immersed in the solution. The composite containing 40%
TTCP plus 30% glass particles were selected, because it
had a relatively high strength and ion release. The speci-
mens were immersed for 28 days in three solutions at pH
of 7, 5.5, and 4, respectively. Then, the flexural strength
and elastic modulus were measured, as described below.
The purpose of Group 4 was to further increase the
amount of Ca and PO4 ion release, by increasing the TTCP
filler level to 50% (from 40% in Groups 2 and 3). The ra-
tionale was that the previous groups showed that the
TTCP-glass composite had much higher strength than a
control material that had ion release. Therefore, there was
room to slightly reduce the glass filler level, thereby
334 XU AND MOREAU

increasing the TTCP level. Three composites were made, method (DMS-80 UV-visible, Varian, Palo Alto, CA) using
with glass co-filler levels of 20%, 25%, and 27%, respec- known standards and calibration curves.26,28,42
tively (Hence TTCP 1 glass filler mass fraction 5 70%, One-way and two-way ANOVA were performed to
75%, and 77%, respectively). Glass filler levels higher than detect the significant effects of the experimental variables.
27% were not used because the composite paste became Tukey’s multiple comparison test was used to compare the
dry and difficult to mix. measured data at a p value of 0.05.
A resin-modified glass ionomer (Vitremer, 3M ESPE,
St. Paul, MN) was used as a control for mechanical proper-
RESULTS
ties of specimens immersed in solutions at different pH.
Vitremer is a two-part, powder/liquid composition, and the
Figure 1 plots the results from Group 1 on the effects of
powder is a radiopaque fluoroaluminosilicate glass. The liq-
TTCP filler level on composite mechanical properties
uid is a light sensitive, aqueous solution of a modified pol-
(Mean 6 SD; n 5 6). No glass particles were used. Incor-
yalkenoic acid (Lot # 20081,028, expiration date 2011–07,
Shade B2). Recommended applications include Class III
and V restorations, restoration of root caries lesions, Class
I and II restorations in primary teeth, and core buildup.
Following manufacturer’s recommendation, two scoops of
powder and two drops of liquid yielded a paste that was
filled into the mold. Each component was weighed, indicat-
ing a powder/liquid mass ratio (g/g) of 2.5/1. Specimens
were photo-cured (Triad-2000) for 1 min on each open side
of the specimen using the same 2 mm 3 2 mm 3 25 mm
molds, then incubated at 378C for 24 h before immersion
and mechanical testing.

Mechanical Testing
Flexural strength and elastic modulus were measured using
a three-point flexural test with a 20 mm span at a cross-
head-speed of 1 mm/min on a computer-controlled Univer-
sal Testing Machine (5500R, MTS, Cary, NC). The flexural
strength of the composite was calculated by S 5 3PmaxL/
(2bh2), where Pmax is the maximum load on the load-dis-
placement curve, L is flexure span, b is specimen width,
and h is specimen thickness.40 The elastic modulus was
calculated by E 5 (P/d)(L3/[4bh3]), where the load P di-
vided by the corresponding displacement d is the slope of
the load-displacement curve in the linear elastic region.41

Ca and PO4 Ion Release

A sodium chloride (NaCl) solution (133 mmol/L) was buf-
fered to three different pHs: pH 4 with 50 mmol/L lactic
acid, pH 5.5 with 50 mmol/L acetic acid, and pH 7 with 50
mmol/L HEPES. Following previous studies,30–32 three
specimens of 2 mm 3 2 mm 3 12 mm were immersed
in 50 mL of solution at each pH, yielding a specimen vol-
ume/solution of 2.9 mm3/mL. This compared to a specimen
volume per solution of 3.0 mm3/mL in a previous
study.26 For each solution, the concentrations of Ca and
PO4 released from the specimens were measured at the fol- Figure 1. Effects of TTCP filler level on composite mechanical
lowing immersion times: 1 day, 3 days, 7 days, 14 days, 21 properties, from Group 1. Only TTCP was incorporated into the
resin; no glass particles were used in the resin. The TTCP compo-
days, and 28 days. At each time period, aliquots of 0.5 mL sites were photo-cured. Each value is the mean of six measure-
were removed and replaced by fresh solution. The aliquots ments with the error bar showing one standard deviation (Mean 6
were analyzed for Ca and PO4 via a spectrophotometric SD; n 5 6).

Journal of Biomedical Materials Research Part B: Applied Biomaterials

 DENTAL CALCIUM PHOSPHATE COMPOSITE
Figure 2. Effects of glass filler reinforcement on composite me-
chanical properties, from Group 2. The TTCP level was the same at
40%, and the glass filler level was varied. Total fillers 5 TTCP 1
glass particles. The TTCP-glass composites were photo-cured.
Increasing the glass filler level significantly increased the composite
strength and elastic modulus (p \ 0.05). Each value is Mean 6 SD;
n 5 6.
poration of TTCP significantly decreased the flexural
strength (ranging from about 50–60 MPa), compared to the
95 6 1 MPa of the unfilled resin (p \ 0.05). Varying the
TTCP level from 10 to 70% did not significantly change
the strength (p [ 0.1). The composite elastic modulus was
significantly increased with increasing the TTCP filler level
as the paste became stiffer (p \ 0.05).
Figure 2 plots mechanical properties of Group 2 on the
effects of glass filler reinforcement, while the TTCP mass
fraction in the resin was fixed at 40%. Increasing the glass
Journal of Biomedical Materials Research Part B: Applied Biomaterials
335
filler level increased the strength (p \ 0.05). Flexural
strength at 20% and 30% glass were (92 6 6) MPa and
(99 6 18) MPa, respectively. Both values were higher than
the (54 6 20) MPa at 0% glass (p \ 0.05). While the
strengths were not significantly different from 10% glass to
35% glass (p [ 0.1), the elastic modulus was monotoni-
cally increased, reaching 10.9 6 0.5 GPa at 30% glass
(Total filler mass fraction 5 40% TTCP 1 30% glass 5
70%).
Figure 3 plots Ca and PO4 ion release for the composite
containing 40% TTCP and 30% glass. It was selected
because it had good strength and elastic modulus, and the
composite paste was relatively easily mixed. Two-way
ANOVA showed significant effects of solution pH and
immersion time, with a significant interaction between the
two variables (p \ 0.05). Lowering the pH substantially
increased the amount of ion release. At 28 days, the
released Ca concentration (Mean 6 SD; n 5 3) was 4.61
6 0.18 mmol/L at pH of 4, much higher than 1.14 6 0.07
mmol/L at pH of 5.5, and 0.27 6 0.01 mmol/L at pH of 7
(p \ 0.05).
At 28 days, the PO4 concentration was 2.14 6 0.14
mmol/L at pH of 4, higher than 0.36 6 0.01 mmol/L at pH
of 5.5, and 0.10 6 0.01 mmol/L at pH of 7 (p \ 0.05).
Figure 4 plots the results from Group 3 on the effect of
solution pH on mechanical properties of the immersed
specimens. The TTCP composite contained 40% TTCP and
30% glass, which was the same as that in Figure 3. Its
strength was 79 6 13 MPa after immersion for 28 days at
pH 4, 83 6 13 MPa at pH 5.5, and 62 6 11 MPa at pH 7.
These results were not significantly different from each
other (p [ 0.1). However, these strength values were lower
than the 99 6 18 MPa for specimens without immersion
(Figure 2) (p \ 0.05).
For Vitremer, the strengths were 29 6 4 MPa, 25 6 3
MPa, and 30 6 4 MPa, at pH of 4, 5.5, and 7, respectively.
They were not significantly different from each other (p [
0.1). However, the strength of the TTCP-glass composite
was significantly higher than that of Vitremer at each pH
(p \ 0.05). The rectangular box at the right axis of Figure
4 indicates the reported strengths of previous CaP materi-
als. Previous studies reported a biaxial flexural strength of
40–50 MPa for CaP materials before immersion; the
strength decreased to 10–20 MPa after 90 days of immer-
sion at neutral pH.28,29 Other studies reported that the
strength of the ACP-composite decreased to about 40 MPa
after 11 days of immersion at neutral pH.26,27 The elastic
modulus of the TTCP-glass composite ranged from 8 to 9.6
GPa, and that of Vitremer ranged from 7.9 to 9.5 GPa,
which were not significantly different from each other (p [
0.1).
Figure 5 plots the results from Group 4, in which the
TTCP filler level was increased to 50% (higher than the
40% TTCP in Figure 2). The purpose was to increase the
TTCP filler level for higher Ca and PO4 release, without
compromising the composite mechanical properties. Indeed,
336 XU AND MOREAU
Figure 3. Ca and PO4 ion release from composite containing 40%
TTCP and 30% glass. Lowering the pH substantially increased the
amount of ion release. Each value is Mean 6 SD; n 5 3. [Color fig-
ure can be viewed in the online issue, which is available at www.
interscience.wiley.com.]
the strengths of the experimental composites represented in
Figure 5 matched the strengths of those shown in Figure
2(A) (p [ 0.1). In Figure 5(A), the flexural strength (Mean
6 SD; n 5 6) was 92 6 20 MPa, 77 6 9 MPa, and 95 6
22 MPa, at 20, 25, and 27% glass, respectively. They were
not significantly different from each other, and neither was
the elastic modulus [Figure 5(B)] (p [ 0.1). However, the
resin paste was drier and more difficult to mix at 50%
TTCP plus 25% or 27% glass. The paste at 50% TTCP and
20% glass was relatively easier to mix. Therefore, the com-
posite with 50% TTCP and 20% glass was selected for Ca
and PO4 release measurement in Figure 6.
Figure 6 plots Ca and PO4 release from the composite
with 50% TTCP and 20% glass. Compared with Figure 3
for the composite with 40% TTCP, increasing the TTCP
filler mass fraction to 50% significantly increased the Ca
and PO4 release (p \ 0.05). pH also had a significant
effect. At 28 days, the Ca concentration was 9.85 6 0.13
mmol/L at pH of 4, much higher than 1.39 6 0.03 at pH
of 5.5, and 0.37 6 0.02 at pH of 7 (p \ 0.05). At 28 days,
the PO4 concentration was 5.40 6 0.34 mmol/L at pH of
4, higher than 0.57 6 0.03 at pH of 5.5, and 0.16 6 0.07
at pH of 7 (p \ 0.05).
DISCUSSION
The methodology of incorporating a reinforcing filler and a
Ca and PO4 ion-releasing filler into the same resin matrix
showed promise in the development of load-bearing, caries-
inhibiting dental composites. Previous studies used
whiskers for reinforcement and yielded a whitish but rela-
tively opaque paste, which may be suitable for load-bearing
posterior restorations.30–32 In the present study, a novel
TTCP-glass composite was developed using ball-milled
fine TTCP particles, esthetic dental glass particles, and a
photo-cured resin. The TTCP provided Ca and PO4 ion
release from the composite to inhibit caries; the glass fillers
provided the needed mechanical reinforcement. The flex-
Figure 4. Effect of solution pH on mechanical properties of
immersed specimens, from Group 3. Specimens were immersed for
28 days, in solutions with pH of 7, 5.5, and 4, respectively. The box
at the right axis indicates the reported strength range of previous
Ca-PO4 materials immersed at neutral pH.26–29 Varying the solution
pH from 4 to 7 had only minor effects on the strength and elastic
modulus of TTCP-glass composite and Vitremer. The composite
with 40% TTCP and 30% glass had much higher strength than
Vitremer and previously-reported Ca-PO4 materials. Each value is
Mean 6 SD; n 5 6. [Color figure can be viewed in the online issue,
which is available at www.interscience.wiley.com.]
Journal of Biomedical Materials Research Part B: Applied Biomaterials
 DENTAL CALCIUM PHOSPHATE COMPOSITE 337

strated that this dual-filler method increased the flexural

strength of the TTCP composite from about 50 MPa to 90
MPa (Figure 2). In addition, the elastic modulus was
increased by 2–3 fold.
In comparison with previous studies, the amorphous cal-
cium phosphate (ACP) composite had a flexural strength of
(56 6 16) MPa for specimens without immersion.43
Another CaP composite had strength of 40–60 MPa for
specimens without immersion.29 Therefore, the flexural
strength of 90 MPa of the new photo-cured TTCP-glass

Figure 5. Group 4 with a TTCP filler level of 50% (higher than the
40% TTCP in Figure 2), reinforced with various glass filler amounts.
The purpose was to increase the TTCP filler level for increased Ca
and PO4 release, without compromising the mechanical properties.
Horizontal line indicates values that are not significantly different
from each other (p [ 0.1). The strengths of Figure 5 were similar to
those in Figure 2 (p [ 0.1). Each value is Mean 6 SD; n 5 6. [Color
figure can be viewed in the online issue, which is available at
www.interscience.wiley.com.]

ural strength of the TTCP composite without glass was

about 50–60 MPa, about 1/2 that of the unfilled resin
(Figure 1), which was similar to previous CaP compo-
sites.26,28 CaP fillers did not reinforce the resin, likely
because these fillers were not strong mechanically, and
they were not silanized hence did not bond chemically to
the resin. A recent study showed that silanization of CaP
fillers did not increase the strength of the composite,32
likely because the silane did not bond to CaP fillers. Fur- Figure 6. Ca and PO4 release from photo-cured composite contain-
thermore, silanization of CaP fillers was not desirable ing 50% TTCP and 20% glass (Mean 6 SD; n 5 3). Increasing the
TTCP fillers to 50% significantly increased the Ca and PO4 release
because it reduced the Ca and PO4 ion release.32 One (as compared to the release at 40% TTCP in Figure 3). [Color figure
approach to overcome this drawback was to incorporate can be viewed in the online issue, which is available at www.
glass co-fillers for reinforcement. The present study demon- interscience.wiley.com.]

Journal of Biomedical Materials Research Part B: Applied Biomaterials

338 XU AND MOREAU
composite was higher than the strengths of previous Ca and
PO4 releasing restoratives.
Immersion for a month in solutions at pH of 7, 5.5, and
4 reduced the composite flexural strength, while the varia-
tion in solution pH did not have a significant effect on the
composite strength. The photo-cured TTCP-glass composite
had an average strength (for specimens immersed at all
three pH) of 75 MPa, about 25% lower than the strength of
specimens before immersion. The strength of the photo-
cured TTCP-glass composite was two-fold higher than the
commercial fluoride releasing control (Vitremer). In com-
parison, a previously-reported CaP material had a flexural
strength of 10–20 MPa after 90 days of immersion at neu-
tral pH.29 The strength of the ACP-composite decreased to
40 MPa after 11 days of immersion at neutral pH.26 These
strengths were similar to that of Vitremer, hence these CaP
materials have the potential to be useful in low-load-bear-
ing restorations. In comparison, the new photo-cured
TTCP-glass composite’s average strength of 75 MPa after
immersion was much higher. This may enable the ion-
releasing composite to be used in higher load-bearing resto-
rations. The higher strength was likely because the new
TTCP-glass composite relied on dental glass fillers for rein-
forcement, while previous CaP materials relied solely on
the CaP fillers for reinforcement, without a glass co-fil-
ler.26–29 Therefore, the photo-cured TTCP-glass composite
is expected to have a better long-term durability than previ-
ous CaP composites that do not have a stable reinforcement
phase. Future study will investigate the long-term water-
aging and wear behavior of the new TTCP-glass composite.
Further study should also examine the cyclic fatigue prop-
erties and fracture toughness using notched specimens for
these Ca and PO4 ion-releasing composites.4,15,17,39
As shown in Figure 3, the photo-cured TTCP-glass com-
posite was ‘‘smart’’ and dramatically increased the Ca and
PO4 release when the pH was reduced from neutral to a
cariogenic pH of 4. It is generally accepted that the local
plaque pH of [ 6 is the safe area, pH of 6.0–5.5 is the
potentially cariogenic area, and pH of 5.5–4 is the cario-
genic area for cavity formation.33,34 It is advantageous that
the TTCP-glass composite could substantially increase Ca
and PO4 release at lower pH, when these ions are most
needed to combat caries. In contrast, the ion release was
minimal at neutral pH, so that these ions would not be
wasted at neutral pH, and the release capability of the
smart composite would not be quickly exhausted. In several
previous studies, the release of fluoride and chlorhexidine
from restoratives at neutral and acidic pH was measured,
which showed more release at lower pH.44–46 Other studies
on CaP composites reported Ca and PO4 release at neutral
pH only, without reporting release at cariogenic pH.26–32 A
recent study from our laboratory reported Ca and PO4
release at different pH, but that composite was relatively
opaque and could not be photo-cured. On the basis of our
literature search, the present study is the first report on a
photo-cured ‘‘smart’’ composite with Ca and PO4 release,
showing a needed, substantial increase in ion release at car-
iogenic pH.
Comparing Figure 3 with Figure 6 indicates that when
the TTCP mass fraction in the composite was increased
from 40 to 50%, the Ca and PO4 release was significantly
increased. A previous study investigated the effect of CaP
filler level on ion release, using another CaP compound.31
It was shown that the ion release increased with increasing
filler level at a rate faster than being linear.31 For example,
when the CaP filler level was doubled, the ion release was
more than doubled. This was because increasing the CaP
filler level not only increased the source of ion release, it
also increased the interfaces in the resin which served as
relatively easier passageways for diffusion of water and
ions.31 This is likely why in the present study, increasing
the TTCP by a mere 10% substantially increased the ion
release.
In previous studies, the ACP-composites released Ca
and PO4 ions to yield a Ca concentration of 0.3–1.0 mmol/
L, and a PO4 concentrations of 0.2–0.7 mmol/L.26 Another
study on remineralizing CaP cement reported a Ca concen-
tration of 0.5 mmol/L, and a PO4 concentration of 0.1
mmol/L, measured in a similar manner.28 It was shown that
when Ca and PO4 were released, they reprecipitated to
form hydroxyapatite outside the composite and inside the
tooth lesions, significantly increasing the mineral content of
the lesion, thereby remineralizing the lesion.25,28 The Ca
and PO4 concentrations released from the new TTCP-glass
composite were relatively high. This suggests that the
mechanically-stronger, photo-cured TTCP-glass composite
might also effectively remineralize tooth lesions. Further
studies should investigate the in situ caries inhibition capa-
bility of the smart TTCP-glass composite.
Regarding potential clinical applications, the composite
with 40% TTCP and 30% glass could be used in load-bear-
ing restorations, for which the current CaP composites and
resin-modified glass ionomer restoratives are mechanically
too weak. The composite with 50% TTCP and 20% glass,
with a higher Ca and PO4 releasing capability, could be
used in treatments where complete removal of caries tissue
is contra-indicated, in teeth where carious lesions are be-
ginning to occur, and for patients at high risk for dental
caries including those receiving radiation treatments or
with dry mouth. Further studies are needed to explore these
applications and the efficacy of the photo-cured smart
TTCP-glass composite.
SUMMARY
Currently-available posterior composites and hybrid compo-
sites can be used as stress-bearing restorations, but they
generally do not release Ca, PO4, or F ions. On the other
hand, restoratives that do release Ca, PO4, or F ions are rel-
atively weak and cannot be used in large stress-bearing
restorations. Therefore, there is a need to develop new
composites that are mechanically strong while at the same
Journal of Biomedical Materials Research Part B: Applied Biomaterials
 DENTAL CALCIUM PHOSPHATE COMPOSITE
time have sustained release of Ca, PO4, and F ions to in-
hibit caries. In the present study, a new calcium phosphate
composite was developed using a photo-cured Bis-GMA/
TEGDMA resin, esthetic dental glass particles, and ball-
milled fine TTCP particles. The flexural strength of the
TTCP-glass composite was two-fold higher than previ-
ously-known CaP composites and a resin-modified glass
ionomer. The photo-cured TTCP-glass composite was
‘‘smart’’ and increased the Ca and PO4 ion release by an
order of magnitude, when the pH was reduced from neutral
to a cariogenic pH of 4, when these ions are most needed
to inhibit tooth caries. Decreasing the solution pH did not
significantly decrease the mechanical properties of the com-
posite. The photo-cured, smart CaP composite, with me-
chanical properties higher than those of previous Ca, PO4,
and F releasing restoratives, may have potential to provide
the necessary combination of load-bearing and caries-inhib-
iting capabilities.
The authors thank Dr. James H. Yen and William F. Guthrie of
the Statistical Engineering Division of the National Institute
of Standards and Technology (NIST) for help with statistical
analysis. They thank Dr. Laurence C. Chow, Dr. Shozo Takagi,
Dr. Sabine Dickens, Dr. Drago Skrtic, and Dr. Limin Sun of the Paf-
fenbarger Research Center of the American Dental Association, and
Dr. Joseph M. Antonucci of NIST for discussions. They also thank
Esstech (Essington, PA) for kindly providing the resin monomers.
REFERENCES
1. American Dental Association (ADA). The 1999 Survey of
Dental Services Rendered. Chicago: ADA Survey Center;
2002.
2. Ferracane JL. Current trends in dental composites. Crit Rev
Oral Biol Med 1995;6:302–318.
3. Bayne SC, Thompson JY, Swift EJ, Stamatiades P, Wilkerson
M. A characterization of first-generation flowable composites.
J Am Dent Assoc 1998;129:567–577.
4. Drummond JL, Bapna MS. Static and cyclic loading of fiber-
reinforced dental resin. Dent Mater 2003;19:226–231.
5. Imazato S. Review: Antibacterial properties of resin compo-
sites and dentin bonding systems. Dent Mater 2003;19:449–
457.
6. Lu H, Stansbury JW, Bowman CN. Impact of curing protocol
on conversion and shrinkage stress. J Dent Res 2005;84:
822–826.
7. Wan Q, Sheffield J, McCool J, Baran GR. Light curable den-
tal composites designed with colloidal crystal reinforcement.
Dent Mater 2008;24:1694–1701.
8. Stansbury JW. Cyclopolymerizable monomers for use in den-
tal resin composites. J Dent Res 1990;69:844–848.
9. Eick JD, Byerley TJ, Chappell RP, Chen GR, Bowles CQ,
Chappelow CC. Properties of expanding SOC/epoxy copoly-
mers for dental use in dental composites. Dent Mater 1993;
9:123–127.
10. Ferracane JL, Mitchem JC. Properties of posterior composites:
Results of round robin testing for a specification. Dent Mater
1994;10:92–99.
11. Loza-Herrero MA, Rueggeberg FA, Caughman WF, Schuster
GS, Lefebvre CA, Gardner FM. Effect of heating delay
on conversion and strength of a post-cured resin composite.
J Dent Res 1998;77:426–431.
Journal of Biomedical Materials Research Part B: Applied Biomaterials
339
12. Watts DC, Marouf AS, Al-Hindi AM. Photo-polymerization
shrinkage-stress kinetics in resin-composites: Methods devel-
opment. Dent Mater 2003;19:1–11.
13. Krämer N, Garcı́a-Godoy F, Reinelt C, Frankenberger R.
Clinical performance of posterior compomer restorations over
4 years. Am J Dent 2006;19:61–66.
14. Tyas M. Correlation between fracture properties and clinical
performance of composite resins in posterior teeth. Aust Dent
J 1990;35:46–49.
15. Ferracane JL, Berge HX. Fracture toughness of experimental
dental composites aged in ethanol. J Dent Res 1995;74:1418–
1423.
16. Ruddell DE, Maloney MM, Thompson JY. Effect of novel fil-
ler particles on the mechanical and wear properties of dental
composites. Dent Mater 2002;18:72–80.
17. Drummond JL. Degradation, fatigue, and failure of resin den-
tal composite materials. J Dent Res 2008;87:710–719.
18. Watts DC, Issa M, Ibrahim A, Wakiaga J, Al-Samadani K,
Al-Azraqi M, Silikas N. Edge strength of resin-composite
margins. Dent Mater 2008;24:129–133.
19. Sarrett DC. Clinical challenges and the relevance of materials
testing for posterior composite restorations. Dent Mater
2005;21:9–20.
20. Sakaguchi RL. Review of the current status and challenges
for dental posterior restorative composites: Clinical, chemis-
try, and physical behavior considerations. Dent Mater
2005;21:3–6.
21. Mjör IA, Moorhead JE, Dahl JE. Reasons for replacement of
restorations in permanent teeth in general dental practice. Int
Dent J 2000;50:361–366.
22. Frost PM. An audit on the placement and replacement of
restorations in a general dental practice. Prim Dent Care
2002;9:31–36.
23. Deligeorgi V, Mjor IA, Wilson NH. An overview of reasons
for the placement and replacement of restorations. Prim Dent
Care 2001;8:5–11.
24. Jokstad A, Bayne S, Blunck U, Tyas M, Wilson N. Quality of
dental restorations. FDI Commision Projects 2–95. Int Dent J
2001;51:117–158.
25. Skrtic D, Hailer AW, Takagi S, Antonucci JM, Eanes ED.
Quantitative assessment of the efficacy of amorphous calcium
phosphate/methacrylate composites in remineralizing caries-
like lesions artificially produced in bovine enamel. J Dent Res
1996;75:1679–1686.
26. Skrtic D, Antonucci JM, Eanes ED. Improved properties of
amorphous calcium phosphate fillers in remineralizing resin
composites. Dent Mater 1996;12:295–301.
27. Skrtic D, Antonucci JM, Eanes ED, Eichmiller FC,
Schumacher GE. Physiological evaluation of bioactive poly-
meric composites based on hybrid amorphous calcium phos-
phates. J Biomed Mater Res 2000;53B:381–391.
28. Dickens SH, Flaim GM, Takagi S. Mechanical properties and
biochemical activity of remineralizing resin-based Ca-PO4
cements. Dent Mater 2003;19:558–566.
29. Dickens SH, Flaim GM, Floyd CJE. Effect of resin composi-
tion on mechanical and physical properties of calcium phos-
phate filled bonding systems. Polymer Prepr 2004;45:329–
330.
30. Xu HHK, Sun L, Weir MD, Antonucci JM, Takagi S, Chow
LC. Nano dicalcium phosphate anhydrous-whisker composites
with high strength and Ca and PO4 release. J Dent Res
2006;85:722–727.
31. Xu HHK, Weir MD, Sun L, Takagi S, Chow LC. Effect
of calcium phosphate nanoparticles on Ca-PO4 composites.
J Dent Res 2007;86:378–383.
32. Xu HHK, Weir MD, Sun L. Dental nanocomposites with Ca-
PO4 release: Effects of reinforcement, dicalcium phosphate
particle size and silanization. Dent Mater 2007:23:1482–1491.
340 XU AND MOREAU
33. Hefferren JJ, Koehler HM. Foods, Nutrition and Dental Health.
Park Forest South, IL: Pathotox Publishers; 1981. p 138.
34. Thylstrup A, Fejerskov O. Textbook of Cariology. Copenha-
gen, Denmark: Munksgaard; 1986. pp 145–146.
35. Xu HHK, Weir MD, Sun L. Calcium and phosphate ion
releasing composite: Effect of pH on release and mechanical
properties. Dent Mater 2009;25:535–542.
36. Chow LC. Calcium phosphate cements: Chemistry, properties,
and applications. Mater Res Symp Proc 2000;599:27–37.
37. Xu HHK, Weir MD, Simon CG. Injectable and strong nano-
apatite scaffolds for cell/growth factor delivery and bone
regeneration. Dent Mater 2008;24:1212–1222.
38. Xu HHK. Long-term water aging of whisker-reinforced poly-
mer-matrix composites. J Dent Res 2003;82:48–52.
39. Xu HHK, Quinn JB, Giuseppetti AA. Wear and mechanical
properties of nano-silica-fused whisker composites. J Dent
Res 2004;83:930–935.
40. ISO/FDIS 4049. Dentistry: Polymer-Based Fillings, Restora-
tive and Luting Materials, 3rd ed. Geneva, Switzerland: Inter-
national Organization for Standardization; 2000.
41. ASTM D 790–03. Standard Test Methods for Flexural Proper-
ties of Unreinforced and Reinforced Plastic and Electrical
Insulating Materials. West Conshohocken, PA: ASTM Inter-
national; 2004.
42. Vogel GL, Chow LC, Brown WE. A microanalytical proce-
dure for the determination of calcium, phosphate and fluoride
in enamel biopsy samples. Caries Res 1983;17:23–31.
43. O’Donnell JNR, Antonucci JM, Skrtic D. Mechanical proper-
ties of amorphous calcium phosphate composites. J Dent Res
2005;84 (IADR Abstract No. 586).
44. Carey CM, Spencer M, Gove RJ, Eichmiller FC. Fluoride
release from a resin-modified glass-ionomer cement in a con-
tinuous-flow system: Effect of pH. J Dent Res 2003;82:829–
832.
45. Anusavice KJ, Zhang NZ, Shen C. Effect of CaF2 content on
rate of fluoride release from filled resins. J Dent Res 2005;
84:440–444.
46. Anusavice KJ, Zhang NZ, Shen C. Controlled release of chlo-
rhexidine from UDMA-TEGDMA resin. J Dent Res 2006;
85:950–954.
Journal of Biomedical Materials Research Part B: Applied Biomaterials